GB2160538A - Ionene-type polymers - Google Patents

Ionene-type polymers Download PDF

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Publication number
GB2160538A
GB2160538A GB08415965A GB8415965A GB2160538A GB 2160538 A GB2160538 A GB 2160538A GB 08415965 A GB08415965 A GB 08415965A GB 8415965 A GB8415965 A GB 8415965A GB 2160538 A GB2160538 A GB 2160538A
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GB
United Kingdom
Prior art keywords
methyl
lonene
odd number
attached
type polymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB08415965A
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GB2160538B (en
GB8415965D0 (en
Inventor
Joseph Gabriel Fenyes
John Dominic Pera
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Buckman Laboratories Inc
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Buckman Laboratories Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US06/414,108 priority Critical patent/US4506081A/en
Priority to NZ202707A priority patent/NZ202707A/en
Priority to ZA829230A priority patent/ZA829230B/en
Priority to DE19823247536 priority patent/DE3247536A1/en
Priority to CA000418563A priority patent/CA1197509A/en
Priority to FR8222118A priority patent/FR2532646B1/en
Priority to AU91997/82A priority patent/AU560802B2/en
Priority to BE0/209953A priority patent/BE895685A/en
Priority to JP58021405A priority patent/JPS5944350A/en
Priority to AR292271A priority patent/AR231124A1/en
Priority to IT47857/83A priority patent/IT1165578B/en
Priority to MX197623A priority patent/MX166612B/en
Priority to GB08319310A priority patent/GB2126579B/en
Priority to BR8304165A priority patent/BR8304165A/en
Priority to CA000456480A priority patent/CA1241653A/en
Priority to AU29581/84A priority patent/AU566275B2/en
Priority to NL8401968A priority patent/NL8401968A/en
Application filed by Buckman Laboratories Inc filed Critical Buckman Laboratories Inc
Priority to GB08415965A priority patent/GB2160538B/en
Priority to FR8410019A priority patent/FR2566414B1/en
Priority to DE3423703A priority patent/DE3423703C2/en
Priority to BE0/213246A priority patent/BE900050A/en
Priority to JP59140425A priority patent/JPH0662514B2/en
Priority to IT48577/84A priority patent/IT1177902B/en
Publication of GB8415965D0 publication Critical patent/GB8415965D0/en
Priority to BR8403882A priority patent/BR8403882A/en
Publication of GB2160538A publication Critical patent/GB2160538A/en
Application granted granted Critical
Publication of GB2160538B publication Critical patent/GB2160538B/en
Expired legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B01D17/047—Breaking emulsions with separation aids
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
    • C07C275/06—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
    • C07C275/14—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines
    • C08G73/0213—Preparatory process
    • C08G73/0226—Quaternisation of polyalkylene(poly)amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0633—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/173—Macromolecular compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/467—Compounds containing quaternary nitrogen atoms derived from polyamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/61—Polyamines polyimines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
    • D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/56—Polyamines; Polyimines; Polyester-imides

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Abstract

Ionene-type polymers having the structure <IMAGE> wherein R'' is <IMAGE> either R and the R' groups are identical and each is ethyl, propyl, butyl, hydroxyethyl or hydroxypropyl; or R is methyl and each of the R' groups, which may be the same or different, is methyl, an alkyl or alkenyl group containing 6 to 18 carbon atoms and having 0 to 2 carbon to carbon double bonds or cyclohexyl, with the additional possibilities that two adjacent R's together with the nitrogen atom to which they are attached may be a piperidyl group or R and two adjacent R's together with the nitrogen atom to which they are attached may be a pyridyl group; m is an integer from 2 to 12; and n is an odd number from 1 to 201, the R''s where n is greater than 1 being the same or different, which polymers are of use inter alia as plant growth regulators, microbiocides and for various other uses in, for example the paper and textile industries.

Description

SPECIFICATION lonene-type polymers This invention relates to novel ionene-type polymers which have been capped with tertiary amines and to their use as microbiocides, plant growth regulators, corrosion inhibitors, debonding agents in the manufacture of fluff pulp, softeners, antistatic agents, demulsifiers, andiorto improve dyeability and colour fastness in textiles and paper.
Polymeric compositions have been used in the past in the pulp and paper, textile and water treating industries for the above-mentioned uses but none, however, are entirely satisfactory. Some are useful as retention aids and flocculants but do not provide any of the other desired benefits. lonene-type polymers which are prepared by reacting ditertiary amines with dihalo compounds are typically products with relatively low molecular weights. These products may be effective for controlling microorganisms but hitherto their use as flocculants or as plant growth regulators have been limited. The most versatile cationic polymers are the polyethylenimines which can be manufactured in various molecular weight ranges by the selection of different catalysts and the use of cross-linking reagents. None of the known polyethylenimines are, however, good microbicides.In addition, the manufacture of polyethylenimines requires the use of the very toxic monomer ethylenimine which, in recent years, has been desired as a carcinogen. Severe restrictions have been placed on the handling of this monomer in commercial and industrial plants by government regulatory agencies.
The degradative effect of microorganisms on organic materials is well known. Elimination or inhibition of growth of algae, bacteria, and fungi has been the objective of a large number of research projects and patents. Quaternary ammonium compounds have found utility for the treatment of water used in various commercial and industrial cooling systems and in swimming pools. We have now found that certain particular cationic polymers of the ionene-type are effective against algae, bacteria and fungi in water systems even when used in very low concentrations as well as having a number of other very desirable properties in relation to, interalia, plant growth regulation.
According to one feature of the invention there are provided novel ionene-type polymers having the structure:
wherein R" is
either R and the R' groups are identical and each is ethyl, propyl, butyl, hydroxyethyl or hydroxypropyl; or R is methyl and each of the R' groups, which may be the same or different, is methyl, an alkyl or alkenyl group containing 6 to 18 carbon atoms and having 0 to 2 carbon to carbon double bonds or cyclohexyl with the additional possibilities that two adjacent R's together with the nitrogen atom to which they are attached may be a piperidyl group or R and two adjacent R's together with the nitrogen atom to which they are attached may be a pyridyl group; mis an integer from 2 to 12; and n is an odd number from 1 to 201, the R"s where n is greater than 1 being the same or different.
The polymers of this invention where n is greater than 1 may be prepared using a two-stage procedure which comprises reacting X moles of a dihalogenated compound of formula:
(wherein R" is as defined above with X-1 moles of at least one ditertiary amine, X being an integer of from 2 to 101, in the presence of water and at elevated temperature, and reacting each mole of the precursor thus obtained, in the presence of a solvent, with 2 moles of an appropriate monotertiary amine whereby the desired polymer is obtained.
In the first stage X moles of N, N, N', N'-tetramethyl-N,N'-bis(3-chloro-2-hydroxypropyl)alkane diammonium dichloride, N,N,N',N'-tetramethyl-N,N '-bis(3-chloro-2-hydroxypropyl)diethylether diammonium dich bride, or N,N'-dimethyl-N,N'-bis(3-chloro-2-hydroxypropyl)-piperzinium dichloride is reacted at an elevated temperaure in the presence of water with X-1 moles of a ditertiary amine. We have found that suitable reaction temperatures and times may vary from about 800C to 1 050C and from 1 to 30 hours.
In the second stage, one mole of the precursor obtained in the first stage is reacted in the presence of a solvent with two moles of monotertiary amine generally at a temperature varying from about 250 to 11 00C and for a period varying from about 1 to 30 hours. Suitable solvents are water, water soluble lower alcohols and other polar compounds. The molecular weight of the precursor may be calculated by multiplying X times the molecular weight of the chlorohydroxypropyl substituted ditertiary amine used and adding X-1 times the molecular weight of the second ditertiary amine.
The first stage of the process involves the reaction of an (x,-ditertiary amine with an a,#-dihalogenated alkyl compound. This reaction is known in the chemical literature as a Menschutkin Reaction and is used to prepare relatively low molecular weight polymers which are polymeric quaternary ammonium compounds known as ionene polymers. The molecular weights of these linear ionenes are generally about 50,000 or less.
The polymer chain length can be controlled using the above method of manufacture according to this invention. When two moles of the a ##-dihalocompound (X moles) are reacted with one mole (X-1 mole) of the ditertiary amine, a very short polymer is formed. If the designation A is used for the dihalo compound and B for the ditertiary amine the polymer could then be designated A-B-A. When 5 moles of A and 4 moles of B are reacted the precursor then is A-B-A-B-A-B-A-B-A-. The same general scheme can be used to a maximum of about 101 forA and 100 for B. Regardless of the number of moles of A and B used, there will be a halogen at either end of the precursor polymer. This precursor is then reacted with a monotertiary amine in the second stage to "cap" the ionene with additional quaternary ammonium groups.The nature of the tertiary amine and the length of the precursor polymer chain will determine the properties of the polymers of this invention and permit variation in hydrophilic and hydrophobic properties.
The polymers of this invention where n is 1 may be prepared using just the second stage i.e. by reacting the dihalogenated compound in the presence of a solvent directly with the appropriate monotertiary amine in a molar ratio of 1 mole of dihalogenated compound to 2 moles of monotertiary amine.
The N,N,N'-tetramethyl-N,N'-bis(3-chloro-2-hydroxypropyl)alkane diammonium dichlorides used in the above reactions may be prepared by reacting the dihydrochloride salts of N,N,N',N '-tetramethyl-u,w- alkanediamines wherein the alkane group contains 2 to 12 carbon atoms with two moles of epichlorohydrin.
The other a,#-dichlorndiquaternary ammonium chlorides may be prepared in the same manner from the dihydrochloride salts of 2,2'-oxybis(N,N-dimethylethanamine) and 1,4-dimethylpiperazine, respectively.
Each ditertiary amine used to produce the a,ca-dichlorndiquaternary ammonium compounds is then reacted as the free base with the a,#dichlorn moieties to produce the ionene polymers of the first stage. In this invention it is not necessary that the same ditertiary amine be used in the first stage. That is, the a,o#-dichlorn derivative may be made with one ditertiary amine but reacted with another ditertiary amine or mixtures of ditertiary amines to produce the product of the first stage.
The monotertiary amines used to cap the ionene polymers include aliphatic, alicyclic, alkylaromatic, aromatic and heterocyclic amines. The aliphatic groups may contain one or more carbon to carbon double bonds and may be substituted with hydroxyl groups. Examples of these amines are N,N-dimethyl methanamine (trimethylamine), N,N-diethyl ethanamine (triethylamine), N,N-dimethyl-1octadecanamine(dimethylstearylamine), N,N-dimethyl-1-octadecenamine (dimethyl-oleylamine), N,N dimethyl-1-dodecanamine (dimethyllaurylamine), N,N-dimethyl-1-tetradecanamine (dimethylmyristylamine), N,N-dimethyl-1-hexadecanamine (dimethylpalmitylamine), N- methyl-N-octadecyl-1octadecanamine (methyldistearylamine( N-decyl-N-methyl-1-decanamine (didecylmethylamine), methyldicocoamine, methyl di-hydrogenated tallow amine, 1-chloro-3-(dimethylamino)-2-propanol, pyridine, 2,2',2"nitrilotris(ethanol) (triethanolamine), 2-(dimethylamino)ethanol, 1,1 ',1"-nitrilotris-2- propanol(triisopropanolamine), N,N-bis(1 -methylethyl)-2-prnpanamine, N,N-dimethylcyclohexylamine and N-methylpiperidine.
A very important aspect of our invention, if not the most important, is that the polymers claimed herein exhibit remarkable properties as plant growth regulators. As to the importance of this feature with reference to the economy in general and to agriculture in particular, the following comments are pertinent. In 1975 the National Academy of Sciences pointed out that the use of plant-growth regulators may be the cause of the most significant increase in yields yet achieved in agriculture. Plant-growth regulators are used to modify the crop by changing the rate, pattern, or both, of the crop's response to the internal and external factors that governs all stages of crop development from germination through vegetative growth, reproductive development, maturity, and senescense, as well as post-harvest preservation.
Plant growth regulators other than nutrients are usually organic compounds applied directly to a plant to alter its life process or structure in some beneficial way so as to enhance yield, improve quality or facilitate harvesting.
The polymers of the present invention have been found to produce a variety of plant growth regulatory responses when applied to cotton, leguminous crop plants, specifically soybean and other crop plants. Thus, according to a further feature of the invention there is provided a method of regulation of the natural growth and/or development of a crop plant which comprises applying to said plant or its habitat an effective amount of one or more ionene-type polymers according to the invention. Also provided are plant growth regulating compositions comprising, as active ingredient, at least one polymer according to the invention in association with an adjuvant.
In the practice of the invention, the active ingredient can be used alone or in combination with a material referred to in the art as an adjuvant in either liquid or solid form. To prepare plant growth regulating compositions, the active ingredient is mixed with an adjuvant which may include, for example, a diluent, extender, carrier and/or conditioning agent. Thus, the active ingredient can be used with an adjuvant such as a solvent liquid of organic origin, water, a wetting agent, dispersing agent or emulsifying agent or any suitable combination of these.
Typical liquid diluents include, for example, water, alcohols and glycols. The plant growth regulating compositions of this invention usually contain one or more surface-active agents in amounts sufficient to render a given composition readily dispersible in water.
Laboratory tests described in the following Examples 68 and 69 demonstrate that these growth regulators are active by showing their effect on ethylene evolution, CO2 fixation and 2 evolution. The fact that the polymers of this invention alter these normal physiological functions of plants proves they are growth regulators.
When the polymers of the invention are used as plant growth regulators generally best results are obtained when about 2-32 oz. of the ionene polymeric compositions are applied per acre of the crop plant (0.14-2.25 kg/h), although beneficial results are obtained when as little as 1 oziacre (0.0025 kg/h) and as much as 64 ozlacre (4.5 kg/h) of the ionene-type polymer are applied. More than 64 oz. per acre (4.5 kg/h) is generally not desirable because of diminished improvement and increased costs. It will be appreciated that the optimum amount depends on many factors such as density of plants, type or variety of plants, efficiency of application, etc.
The plant growth regulators of the invention can be used successfully on a wide variety of plant species.
These regulators are of special value to agriculturally important crops, such as cotton, the grains, the legumes, and numerous vegetable and fruit crops. In addition, these regulators can also be used on ornamentals, house plants, and other plants grown principally or solely for their decorative value.
According to a still further feature of the present invention there is provided a method of inhibiting the growth and/or proliferation of microorganisms selected from algae, bacteria and fungi which comprises contacting said microorganisms with an effective amount of one or more polymers as defined above as well as aqueous systems containing an antimicrobially effective amount of such polymers.
The ionene-type polymers of this invention are soluble in water and also other polar solvents such as alcohols, glycols and dimethylformamide. Concentrations which are suitable for the control of microorganisms vary from 0.5 to 500 ppm based on the weight of the water being treated. For the control of corrosion in aqueous systems, concentrations of 0.5 to 500 ppm based on the weight of water treated are suitable with a preferred concentration range of 0.5 to 50 ppm.
Ayet further feature of the invention is a method of treating cellulose pulp to reduce interfiber bonding, which comprises adding to the cellulose pulp fiber slurry prior to or during the formation of the slurry into a web, an effective amount of one or more polymers as defined above. Such debondingenables a low degree of mechanical strength to be imparted to webs formed from the pulp. As a debonding agent for cellulose pulp, the ionene-type polymers of this invention are generally used in amounts varying from 0.1 to 2.0 parts per 100 parts of cellulose pulp fiber based on the dry weight of the fiber. The softening of textiles, paper or cellulose pulp sheets is achieved with these polymers generally in amounts of 0.1 to 1.0 part per 100 parts of textile fabric, paper, or cellulose pulp based on the dry weight of material treated.
The polymers according to the invention are also of use as demulsifiers to break oil-in-water or water-in-oil emulsions. Suitable concentrations are 0.5 to 500 ppm based on the weight of the emulsion. The polymers may also be used as antistatic agents for textile fabrics, plastics, or paper, suitable quantities of the polymers being from 0.1 to 2.0 parts per 100 parts of material treated. According to yet another feature of the invention there is provided a method of improving the retention of dyes, water-proofing and/or flame-proofing materials in textiles during the finishing thereof, which comprises adding to the finishing system an effective amount of one or more of the polymers according to the invention.To improve the dyeability and colour fastness in textiles and paper, suitable polymer concentrations range from 0.05 to 1.0 part per 100 parts of dry textile fabric or dry paper.
A still further feature of the invention is a method of flocculating solids from an aqueous system containing suspending and/or dissolved solids, which comprises adding to the aqueous system an effective amount of a flocculant comprising one or more of the polymers according to the invention.
In order to disclose the nature of the present invention still more clearly, the following illustrative examples are given. It is to be understood, however, that the invention is not to be limited to the specific conditions or details set forth in these examples except insofar as such limitations are specified in the appended claims.
NOTE: in the following examples, * indicates that water was added to dilute the product to the indicated concentration, ** indicates that the solvent was propylene glycol, and *** indicates that the solvent was a mixture of water and propylene glycol.
EXAMPLE 1 Preparation ofN,N,N',N'4etramethyl-N,N'-bis (3-chloro-2-hydroxypropyl)ethanediammonium dichloride (Precursor A) A 1000 mL four-neck flask equipped with a reflux condenser, mechanical stirrer, thermometer and a dropping funnel was charged with 187.8 g (1.0 mole) of a 61.0 percent aqueous solution of N,N,N',N'tetramethyl-1,2-ethanediamine.The solution was cooled with an ice-water bath and 197.1 g (2 moles) of 37 percent hydrochloric acid was added at such a rate as to keep the temperature below 45 C. To the well-agitated N,N,N',N'4etramethyl-1 2-ethanediamine dihydrochloride solution so obtained, 185.0 g (2.0 moles) of epichlorohydrin was added slowly, taking care that the temperature did not exceed 45 C. After the addition was complete, the temperature was raised to between 60 and 70 C for 30 minutes. At 65.7 percent aqueous solution of the title compound was obtained.
An aliquot of this aqueous solution was treated with four times its volume of acetone. A sticky precipitate formed and the liquid was decanted from it. The residue was dissolved in methanol and the resulting solution was diluted with acetone. The precipitate formed was filtered and dried over P205 under reduced pressure to give a very hydroscopic white solid.
EXAMPLES 2 to 8 Various quantities of the 65.7 percent aqueous solution of N,N,N',N'-tetramethyl-N,N'-bis(3-chloro-2 hydroxypropyl)ethanediammonium dichloride (Precursor A) prepared in Example 1 and varying quantities of N,N,N',N'-tetramethyl-1,2-ethanediamine were refluxed for one hour while being stirred vigorously. The reaction products, polyquaternary ammonium salts, were obtained as aqueous solutions having total solids content as indicated in Table 1.
TABLE 1 Example Precursor Precursor A to Diamine Solids Content Prepared Mole ratio Percent 2 B 2.0 to 1.0 65.8 3 C 4.0 to 3.0 65.8 4 D 6.0 to 5.0 66.9 5 E 8.0to7.0 66.9 6 F 16.0 to 15.0 50.0* 7 G 51.0 to 50.0 50.0* 8 H 101.0 to 100.0 50.0* EXAMPLES 9 to 12 Various quantities of the 65.7 percent aqueous solution of Precursor A prepared in Example 1 were reacted at reflux temperature with a number of tertiary amines at a mole ratio of 2 to 1 of tertiary amine to Precursor A. These reactions include in Table 2.
TABLE 2 Tertiary Time of Solids Example Amine Reaction Content Hours Percent 9 N,N-dimethyl-1- 4 80.5 dodecanamine 10 N,N-dimethyl-1- 4 50.0* octadecanamine 11 2,2',2"-nitrilo- 4 80.2 trisethanol 12 pyridine 24 73.0 13 N-methylpiperidine 6 50.0* EXAMPLE 14 To a vigorously stirred refluxing solution of 50 g (0.12 mole) of Kemamine T-6501 (methyl dicocoamine, having an average molecular weight of 415.5 and supplied by Humko Sheffield Chemical Co.) in 250 mL of acetone, 32.5 g (0.06 mole) of a 69.3 percent aqueous solution of the product of Example 1 was slowly added from a dropping funnel. After the introduction was completed, stirring and refluxing were continued for an additional 5 hours. The acetone solvent was distilled from the reaction mixture and the oily residue, containing 87.9 percent of the desired polyquaternary ammonium salt, was transferred to a container.On cooling, the product became a white, lard-like semisolid and had a limited water solubility.
EXAMPLE 15 To 40.0 g (0.0774 mole) of molten Kemamine T-9701 (methyl di-hydrogenated tallowamine having an average molecular weight of 516.8 and supplied by Humko Sheffield Chemical Co.) maintained between 80 and 95 C, 20.9 g (0.0387 mole) of the Precursor A solution was slowly added while the reaction mixture was vigorously agitated. After stirring and heating for 16 hours, the reaction mixture was cooled and a polyquaternary ammonium salt was obtained as a white, lard-like semisolid containing 89.5 percent solids.
EXAMPLES 16to 20 Various quantities of the 65.8 percent aqueous solution of Precursor B prepared in Example 2 were reacted at reflux temperature with a number of tertiary amines at a mole ratio of 2 to 1 of tertiary amine to Precursor B. These reactions are given in Table 3.
TABLE 3 Tertiary Time of Solids Example Amine Reaction Content Hours Percent 16 N,N-dimethyl-1- 3 77.8 dodecanamine 17 N,N-dimethyl-1- 5 25.0* octadecanamine 18 2,2',2"-nitrilol 5 75.7 trisethanol 19 pyridine 24 73.1 20 N-methylpiperidine 6 50.0* EXAMPLES 21 to 29 In a manner analogous to Examples 16 to 20, solutions of Precursors C to H of Examples 3 to 8 were treated at reflux temperature with tertiary amines. The molar ratio of tertiary amine to Precursor was 2 to 1. The solvents used and the lengths of reaction times for these reactions are given in Table 4.
TABLE 4 Tertiary Time of Solids Example Precursor Amine Solvent Reaction Content Hours Percent 21 C N,N-dimethyl-1- water 4 74.3 dodecanamine 22 C N,N-dimethyl-1- water/propylene 12 25.0** octadecanamine glycol 23 D N,N-dimethyl-1- water/propylene 4 25.0*** udodecanamine glycol 24 D N,N-dimethyl-1- water/propylene 8 25,0*** octadecanamine glycol 25 E N,N-dimethyl-1- water 4 25.0* dodecanamine 26 E N,N-dimethyl-1- water/propylene 6 25.0*** octadecanamine glycol 27 G N,N-dimethyl-1- water 6 50.0* dodecanamine 28 H N,N-dimethyl-1- water 6 50.0* dodecanamine 29 H N,N-dimethyl-1- water/propylene 10 25.0*** octadecanamine glycol EXAMPLE 30 Preparation of N' -dimeth yl-N,N' -bis(3-chloro-2-hydroxyprop yl) piperazinium dichloride (Precursor I) A 5000 mL four-neck round-bottom flask equipped with a reflux condenser, mechanical stirrer, thermometer and a dropping funnel was charged with 1198.5 g (5.0 moles) of a 47.6 percent aqueous solution of 1 A-dimethylpiperazine. The solution was cooled by means of an ice-water bath and 985.5 g (10.0 moles) of 37 percent hydrochloric acid was added at such a rate as to keep the temperature below 45 C. To the well-agitated 1 4-dimethylpiperazine dihydrochloride solution so obtained, 925.2 g (10.0 moles) of epichlorohydrin was added slowly, again at such a rate as to keep the temperature below 45 C. After the addition was completed, the temperature of the reaction mixture was raised to between 600 and 700 C for 30 minutes, followed by another hour at 1000 C. A 59.8 percent solution of N,N'-dimethyl-N,N'-bis(3-chloro-2 hydroxypropyl) piperazinium dichloride was obtained.
EXAMPLES 31 to 33 Various quantities of the 59.8 percent aqueous solution of N,N'-dimethyl-N,N'-bis(3-chloro-2 hydroxypropyl)piperazinium dichloride (Precursor I) prepared in Example 30 and varying quantities of 1,4-dimethylpiperazine were refluxed for 18 hours while being stirred vigorously. The reaction products, polyquaternary ammonium salts, were obtained as aqueous solutions having total solids content as indicated in Table 5.
TABLE 5 Precursor Precursorito 1,4 Example Prepared Dimethylpiperazine Solids Content Mole Ratio Percent 31 J 2 to 1 57.8 32 K 4 to 3 57.1 33 L 5 to 4 57.0 EXAMPLES 34to 37 Various quantities of the 59.8 percent aqueous solution of Precursor I of Example 30 were reacted with a number of tertiary amines at a mole ratio of 2 to 1 of tertiary amine to Precursor I. These reactions are given below in Table 6.
TABLE 6 Tertiary Time of Solids Example Amine Reaction Content Hours Percent 34 N,N-dimethyl-1- 6 76.2 dodecanamine 35 N,N-dimethyl-1- 8 25.0* octadecanamine 36 2,2',2"-nitrilo- 4 72.9 trisethanol 37 N-methylpiperidine 8 50.0 EXAMPLES 38 to 41 Various quantities of the 57.8 percent aqueous solution of Precursor J of Example 31 were reacted at reflux temperature with a number of tertiary amines at a mole ratio of 2 to 1 of tertiary amine to Precursor J. These reactions are given below in Table 7.
TABLE 7 Tertiary Time of Solids Example Amine Reaction Content Hours Percent 38 N,N-dimethyl-1- 6 66.8 dodecanamine 39 N,N-dimethyl-1- 10 25.0** octadecanamine 40 2,2',2"-nitrilo- 4 64.4 trisethanol 41 N-methylpiperidine 8 50.0* EXAMPLES 42to 45 Various quantities of the 57.1 percent aqueous solution of Precursor K of Example 32 were treated at reflux temperature with a number of tertiary amines at a mole ratio of 2 to 1 of tertiary amine to Precursor K. These reactions are included in Table 8.
TABLE 8 Tertiary Time of Solids Example Amine Reaction Content Hours Percent 42 N,N-dimethyl-1- 6 62.9 dodecanamine 43 N,N-dimethyl-1- 10 25.0** octadecanamine 44 2,2',2"-nitrilo- 4 60.7 trisethanol 45 N-methylpiperidine 8 50.or+ EXAMPLES 46to 50 Various quantities of the 57.0 percent aqueous solution of Precursor L of Example 33 were reacted with a number of tertiary amines at a mole ratio of 2 to 1 of tertiary amine to Precursor L. These reactions are given below in Table 9.
TABLE 9 Tertiary Time of Solids Example Amine Reaction Content Hours Percent 46 N,N-dimethyl-1- 6 50.0* dodecanamine 47 N,N-dimethyl-1- 6 50.0* tetradecanamine 48 N,N-dimethyl-1- 6 50.0* hexadecanamine 49 N,N-dimethyl-1- 10 25.0* octadecanamine 50 N-methylpiperidine 8 50.0* EXAMPLE 51 Preparation of N, N, N', N' 4etrameth yl-N,N' -bis-(3-chloro-2-h ydros yprop yl)diethylether diammonium dichloride (Precursor M) A 2000 mLfour-neck round-bottom flask equipped with a reflux condenser, a mechanical stirrer, thermometer and dropping funnel was charged with 160.2 g (1.0 mole) of 2,2'-oxybis(N,Ndimethylethanamine) and 293.9 g water.The vigorously agitated mixture was cooled by means of an ice-water bath while 197.1 g (2.0 moles) of 37 percent hydrochloric acid was introduced at such a rate as to keep the temperature of the reaction mixture below 45 C. The 2,2'-oxybis(N,Ndimethylethanamine)dihydrochloride thus prepared was treated with 185.0 g (2.0 moles) of epichlorohydrin while agitation was maintained and care was taken to keep the temperature below 45"C. After the addition was complete, the reaction mixture was refluxed 6 hours. A 50 percent aqueous solution of the title compound was obtained.
EXAMPLES 52 to 53 Various quantities of the 50.0 percent aqueous solution of N,N,N',N'-tetramethyl-N,N'-bis(3-chloro-2- hydroxypropyl)diethyletherdiammonium dichloride (Precursor M) prepared in Example 51 and varying quantities of 2,2'-oxybis-(N,N-dimethylethanamine) were refluxed for 6 hours while being stirred vigorously.
The reaction products, polyquaternary ammonium salts, were obtained as aqueous solutions having total solids contents as incicated in Table 10.
TABLE 10 Precursor Example Prepared PrecursorM to Diamine Solids Content Mole Ratio Percent 52 N 2 to 1 50.0* 53 0 4 to 3 50.0* EXAMPLES 54to 57 Various quantities of the 50.0 percent aqueous solution of Precursor M prepared in Example 51 were reacted at reflux temperature with a number of tertiary amines at a mole ratio of 2 to 1 of teriary amine to Precursor M. These reactions are indicated in Table 11.
TABLE 11 Tertiary Time of Solids Example Amine Reaction Content Hours Percent 54 N,N-dimethyl-1- 6 66.9 dodecanamine 55 N,N-dimethyl-1- 6 25.00** octadecanamine 56 pyridine 18 68.0 57 2,2',2"-nitrilo- 4 63.1 trisethanol EXAMPLES 58 to 59 Various quantities of the 50.0 percent aqueous solution of Precursor N prepared in Example 52 were reacted at reflux temperature with two tertiary amines at a mole ratio of 2 to 1 of tertiary amine to precursor N. These reactions are given in Table 12.
TABLE 12 Tertiary Time of Solids Example Amine Reaction Content Hours Percent 58 N,N-dimethyl-1- 6 58.8 dodecanamine 59 N,N-dimethyl-1- 6 25.0** octadecanamine EXAMPLES 60 to 63 Various quantities of the 50.0 percent aqueous solution of Precursor 0 prepared in Example 53 were reacted at reflux temperature with a number of tertiary amines at a molar ratio of 2 to 1 of tertiary amine to Precursor O. These reactions are given in Table 13.
TABLE 13 Tertiary Time of Solids Example Amine Reaction Content Hours Percent 60 N,N-dimethyl-1- 6 54.5 dodecanamine 61 N,N-dimethyl-1- 6 25.0** octadecanamine 62 pyridine 18 51.8 63 2,2',2"-nitrilo- 4 53.2 trisethanol EXAMPLE 64 The effect of the novel ionene type polymeric compositions described in the preceding examples on the percentage kill of the bacterium Enterobacteraerogenes was determined using the method described in U.S.
Patent No. 2,881,070 with the modification described in U.S. Patent No.4,054,542. The results are indicated in Table 14.
TABLE 14 Concentration in parts per million requfred for 80 percent kill or greater lonene polymer of Enterobacter aerogenes in a basal from examples salt substrate after 18 hours contact pH 6.0-6.5 pH 7.0-7.5 pH 8.0-8.5 2 2.0 2.0-4.0 4.0 3 1.0 0.5 2.0 9 0.1 0.1 0.1 12 - 0.5 16 1.0 0.5 0.5 20 1.0 0.5 2.0 30 1.0 ~ ~ 31 - 4.0 > 4.0 32 - 2.0 4.0 33 4.0 4.0 34 4.0 4.0 38 2.0 2.0 2.0 41 - 1.0-2.0 0.5 42 2.0 1.0-2.0 2.0 EXAMPLE 65 The effect of one of the ionene-type polymers described in the preceding Examples on the inhibition of the fungi Chaetomium globosum and Penicillium roquefortiwas determined using the method described in U.S.
Patent No. 3,356,706 with the modification described in U.S. Patent No. 4,054,542. The polymer described in Example 16 completely prevented the growth of both fungi at 8 parts per million.
EXAMPLE 66 The effect of some of the ionene-type polymers as described in the preceding examples on the inhibition of the algae Chlorellapyrenoidosa, Chlorococcum hypnosporum, and Phormidium inundatum was determined using the procedure described in Example 2 of U.S. Patent No.3,771,989. The results are included in Table 15.Observations of growth were made after 28 days on the basis of the following Key: 4 = Excellent 3 = Good 2 = Poor 1 = Very poor, scant, questionable 0 = No growth TABLE 15 Concentration in parts per lonene polymer million required for inhibition from examples of growth after 28 days Chiorella Chlorococcum Phormidium pyrenoidosa hypnosporum inundatum 2 4.0 2.0-4.0 > 8.0 3 4.0 2.0 8.0 9 2.0 2.0 2.0 14 8.0 4.0 16 1.0-2.0 1.0 2.0 20 4.0 4.0 > 4.0 31 8.0 8.0 32 1.0-2.0 - 33 2.0 2.0 4.0 34 2.0 2.0 4.0 37 2.0-4.0 4.0 38 2.0-4.0 4.0 41 2.0 2.0 8.0 EXAMPLE 67 The ionene-type polymers of this invention were used in the treatment of wet bleached pine Kraft pulp in the form of an aqueous slurry with a pulp consistency of 0.5 percent.Handsheets were formed from the pulp on a laboratory handsheet machine to produce 20 cm x 20 cm pulp sheets with basis weights of 120 g/m2.
After the sheets were formed, pressed and dried by the standard procedure, the debonding effect was evaluated by determining the fiber-to-fiber internal bonding strength of these sheets by means of a Scott Internal Bond Tester as described in TAPPI UM-403. The debonding effect was expressed as a percentage factor calculated as follows: (Internal Bond Factor = (Internal Bond of Treated Pulp Sheet) x 100 Internal Bond Factor = Internal Bond of Untreated Pulp Sheet Thus, the untreated pulp would have an Internal Bond Factor of 100 and debonded pulp would have an Internal Bond Factor below 100; the lower this factor, the greater the degree of debonding achieved.
Table 16 shows the results obtained with the ionene polymers when they were evaluated by the indicated test method. Treatment rates are in weight percent based on the dry weight of pulp.
TABLE 16 lonene polymer Treatment Rate Internal Bond from examples Percent Factor 9 0.5 70 10 0.5 81 14 0.5 48 38 0.5 78 These results show that the ionene polymers of this invention are good debonding agents, reducing the internal bond strength to as low as 48 percent of the strength of the original untreated pulp.
EXAMPLE 68 The polymer of Example 50 shows outstanding increases in ethylene evolution on soybean and cotton and this polymer is an excellent fruit ripener, cotton boll opener, flower inducer, etc. Reduced ethylene production, as with the polymers of Examples 46,47, and 48, decreases flowering, ripening, and vegetative growth etc.
The effect of some of the novel ionene-type polymers described in the preceding examples on the percent oxygen evolution and 14cm2 uptake by leaf discs was determined according to the following experiment: Cotton and soybean seeds from a single parent plant were germinated in vermiculite moistened with tap water in a controlled environment chamber. Eight to ten days after germination eight 1-cm diameter discs were cut with a cork borer from visually equivalent, fully expanded leaves and placed into a 30mL glass vial.
A small amount of degassed 0.1 M phosphate buffer (pH 6.4) was immediately added to each vial. This solution was infiltrated into the leaf discs by applying an intermittent vacuum of 50 to 75mm Hg, gently decanted, and a fresh 25.0-mL aliquot of the same solution and a magnetic stirring bar were added. A Clark oxygen electrode mounted in a rubber stopper was immediately inserted into each vial, from which air bubbles escaped through a groove along the outside of the stopper. The vial-electrode unit was placed in a Plexiglas water jacket over a magnetic stirrer, which was then started. After equilibration in dim light after 10 minutes, cool white and fluorescent lamps were switched on at either side of the water jacket. Four such vial electrode units were used simultaneously.
This apparatus made it possible to examine aspects of leaf disc activity by measuring net oxygen evolution and net carbon dioxide uptake. Estimates of apparent CO2 uptake could be made using this same apparatus, with the injection of 0.5 mL of a 0.1 millicurie per mole NaH'4CO3 solution to the buffered solution immediately after each vial was sealed. Following the measurement of 2 evolution, the leaf discs were rinsed in tap water, placed into centrifuge tubes containing 2 mL of 5% (w/v) trichloroacetic acid in ethanol and 0.1 g of activated charcoal, and covered with Paraffin. After incubation at 21 to 24 C for 48 hr, the samples were centrifuged at 1000 rcf (relative centrifugal force, or 13000 x G) for 10 minutes. A 0.1 -mL aliquot of the supernatantwas added to a counting vial containing 20 mL of liquid scintillator (4.0 g PPO (2,5-diphenyloxazole), 0.1 g POPOP (1,4-bis [ 2-(5-phenyloxazolyl)Jbenzene), in 700 mLtoluene and 300 mL absolute ethanol) for counting in a liquid scintillation system. The count data obtained were interpreted as residual 14C activity fixed in ethanolic TCA-stable forms. The effect of plant growth regulators on 2 evolution and 14cm2 fixation was measured by adding these chemicals in a 0.25 mL aliquotto the reaction medium at the beginning ofthe 10-minute equilibration.
The results of these tests using the polymers listed are indicated in Table 17.
TABLE 17 On Cotton lonene polymer from examples CO2 Fixation 2 Evolution 50 ppm 100 ppm 250 ppm 50 ppm 100 ppm 250 ppm 46 -7 -17 -17 +49 +12 +10 47 -7 - 8 -17 +48 +12 +10 48 -7 -17 -15 +45 +14 +11 50 +3 - 2 +37 -11 -16 -26 On Soybean 25 ppm 50 ppm 100 ppm 25 ppm 50 ppm 100 ppm 46 +63 +70 +43 -45 -38 -66 47 +65 +70 +43 -45 -38 -66 48 +63 +69 +42 -44 -37 -65 50 - 6 - 3 +10 -25 -14 -45 EXAMPLE 69 The increased CO2 fixation and increased 2 evolution with the polymers of Examples 46,47,48, and 50 have an effect on the nutritional uptake within the plant such as the assimilation of nitrogen for vegetative growth and potassium for fruit maturation.
The effect of some of the novel ionene-type polymers described in the preceding examples on the percent ethylene evolution was determined by the Leaf Disc Method as follows: Leaf discs as obtained for the 2 and 54cm2 tests were submerged in experimental test solution for approximately 20 minutes after which time they were rinsed with deionized water and rapidly blotted and placed into a 4 mL vial and sealed with a serum stopper. After 1, 8, and 24 hours, samples were removed from the vial for ethylene determination. After each sampling time N2 gas was used to flush the vial before setting aside for the next sampling time. Ethylene analysis was made by injecting 1 mL samples from the vials into a Perkin-Elmer gas chromatograph equipped with a 6 ft PoraPak Q, 80 to 100 mesh column.
Detector response to standard ethylene gas was used for reference standards. The ethylene was calculated as mL ethylene/liter cam~2 hil, and comparisons made as percentage changs from non-treatments, positive or negative.
The results of this test using the polymers listed are included in Table 19.
TABLE 18 Ethylene percent increase over control on cotton lonene polymers from examples 50 ppm 100 ppm 250 ppm 46 +15 -25 -10 47 +15 -22 -10 48 +17 -21 -10 50 -19 +90 ++129 Ethylene percent increase over control on soybean 25 ppm 50 ppm 100 ppm 46 -46 -25 -38 47 -43 -22 -36 48 -43 -27 -37 50 +70 +70 +250

Claims (41)

1. lonene-type polymers having the structure
wherein R" is
either R and the R' groups are identical and each is ethyl, propyl, butyl, hydroxyethyl or hydroxypropyl; orR is methyl and each of the R' groups, which may be the same or different, is methyl, an alkyl or alkenyl group containing 6 to 18 carbon atoms and having 0 to 2 carbon to carbon double bonds or cyclohexyl, with the additional possibilities that two adjacent R's together with the nitrogen atom to which they are attached may be a piperidyl group or R and two adjacent R's together with the nitrogen atom to which they are attached may be a pyridyl group; m is an integer from 2 to 12; and n is an odd number from 1 to 201, the R"s where n is greater than 1 being the same or different.
2. lonene-type polymers according to claim 1 wherein R is methyl, one R' attached to a terminal nitrogen is methyl and the other is dodecyl, n is an odd number from 1 to 21 and R" is
3. lonene-type polymers according to claim 1 wherein R is methyl, one R' attached to a terminal nitrogen is methyl and the other is hexadecyl, n is an odd numberfrom 1 to 21 and R" is
4. lonene-type polymers according to claim 1 wherein R and the two adjacent R's together with the nitrogen atom to which they are attached ae a pyridyl group, n is an odd number from 1 to 21 and R" is
5. lonene-type polymers according to claim 1 wherein the two adjacent R' groups together with the nitrogen atom to which they are attached are a piperidyl group, R is methyl, n is an odd number from 1 to 21 and R" is
6.Ionene-type polymers according to claim 1 wherein R and R' are hydroxyethyl, n is an odd number from 1 to 21 and R" is
7. lonene-type polymers according to claim 1 wherein R is methyl, one R' attached to a terminal nitrogen is methyl and the other is dodecyl, n is an odd number from 1 to 21 and R" is
8. lonene-type polymers according to claim 1 wherein R is methyl, one R' attached to a terminal nitrogen is methyl and the other is hexadecyl, n is an odd number from 1 to 21 and R" is
9. lonene-type polymers according to claim 1 wherein R and the two adjacent R's together with the nitrogen atom to which they are attached are a pyridyl group, n is an odd number from 1 to 21 and R" is
10. Ionene-type polymers according to claim 1 wherein the two adjacent R' groups together with the nitrogen atom to which they are attached are a piperidyl group, R is methyl, n is an odd number from 1 to 21 and R" is
11. lonene-type polymers according to claim 1 wherein R and R' are hydroxyethyl, n is an odd number from 1 to 21 and R" is
12. lonene-type polymers according to claim 1 wherein R is methyl, one R' attached to a terminal nitrogen is methyl and the other is dodecyl, n is an odd number from 1 to 21 and R" is
13. lonene-type polymers acording to claim 1 wherein R is methyl, one R' attached to a terminal nitrogen is methyl and the other is hexadecyl, n is an odd number from 1 to 21 and R" is
14. lonene-type polymers according to claim 1 wherein rand the two adjacent R's together with the nitrogen atom to which they are attached are a pyridyl goup, n is an odd number from 1 to 21 and R" is
15. lonene-type polymers according to claim 1 wherein the two adjacent R' groups, together with the nitrogen atom to which they are attached, are a piperidyl group, R is methyl, n is an odd number from 1 to 21 and R" is
16. lonene-type polymers according to claim 1 wherein rand R' are hydroxyethyl, n is an odd number from 1 to 21 and R" is
17.A process for the preparation of an ionene-type polymer according to claim 1 where n is greater than 1 which comprises reacting X moles of a dihalogenated compound of formula:
(where R" is as defined in claim 1) with X-1 moles of at least one ditertiary aine, X being an integer of from 2 to 101, in the presence of water and at elevated temperature, and reacting each mole of the precursor thus obtained, in the presence of a solvent, with 2 moles of an appropriate monotertiary amine whereby the desired polymer is obtained.
18. A process for the preparation of an ionene-type polymer according to claim 1 where n is 1 which comprises reacting each mole of a dihalogenated compound of formula
(where R" is as defined in claim 1) with 2 moles of an appropriate monotertiary amine whereby the desired polymer is obtained.
19. A process for the preparation of an ionene-type polymer according to claim 1 substantially as herein described.
20. A process for the preparation of an ionene-type polymer according to claim 1 substantially as herein described with reference to the Examples.
21. lonene-type polymers according to claim 1 whenever prepared by a process according to any one of claims 17 to 20.
22. A method of flocculating solids from an aqueous system containing suspended and/or dissolved solids, which comprises adding to the aqueous system an effective amount of a flocculant coprising one or more or the polymers according to claim 1.
23. A method of improving the retention of dyes, water-proofing and/or flame-proofing materials in textiles durings the finishing thereof, which comprises adding to the finishing system an effective amount of one or more of the polymers according to claim 1.
24. A method of inhibiting the growth and/or proliferation of microorganisms selected from algae, bacteria and fungie which comprises contacting said microorganisms with an effective amount of one or more polymers according to claim 1.
25. A method of treating cellulose pulp to reduce inter-fiber bonding which comprises adding to the cellulose pulp fiber slurry prior to or during the formation of the slurry into a web, an effective amount of one or more polymers according to claim 1.
26. A method of regulating the natural growth and/or development of a crop plant which comprises applying to said plant or its habitat an effective amount of one or more polymers according to claim 1.
27. A method according to claim 26 wherein the polymer is applied in an amount of from 2-32 oz/acre.
28. Plant growth regulating compositions comprising, as active ingredient, at least one polymer according to claim 1 in association with an adjuvant.
29. An aqueous system which includes an antimicrobially effective amount of a polymer according to claim 1.
30. An aqueous system according to claim 29 containing from 0.5 to 500 ppm by weight of polymer acording to claim 1.
31. An aqueous system according to claim 30 containing from 0.5 to 50 ppm by weight of a polymer according to claim 1.
32. Cellulose pulp, textiles, plastics and paper having incorporated therein from 0.1 to 2.0 parts of a polymer according to claim 1 per 100 parts based on dry weight of the cellulose pulp fiber, textile, plastic or paper.
33. Textiles, paper and cellulose pulp having incorporated therein from 0.1 to 1.0 parts of a polymer according to claim 1 per 100 parts based on dry weight of the textile fabric, paper or cellulose pulp.
34. Oil-in-water and water-in-oil emulsions having incorporated therein from 0.5 to 500 ppm by weight of a polymer according to claim 1.
35. Compositions containing a polymer according to claim 1 substantially as herein described.
36. Compositions containing a polymer according to clim 1 substantially as herein described with reference to the Examples.
37. Products incorporating a polymer according to claim 1 substantially as herein described.
38. Products incorporating a polymer according to claim 1 substantially as herein described with reference to the examples.
39. A method of using a polymer according to claim 1 substantially as herein described.
40. A method of using a polymer according to claim 1 substantially as herein described with reference to the Examples.
41. Each and every novel method, process, compound, composition and product herein disclosed.
GB08415965A 1982-09-02 1984-06-22 Ionene-type polymers Expired GB2160538B (en)

Priority Applications (24)

Application Number Priority Date Filing Date Title
US06/414,108 US4506081A (en) 1982-09-02 1982-09-02 Polymeric quaternary ammonium compounds and their uses
NZ202707A NZ202707A (en) 1982-09-02 1982-12-03 Polymeric quaternary ammonium compounds
ZA829230A ZA829230B (en) 1982-09-02 1982-12-15 Polymeric quaternary ammonium compounds and their uses
DE19823247536 DE3247536A1 (en) 1982-09-02 1982-12-22 POLYQUATERIAL AMMONIUM COMPOUNDS AND METHOD THEREFORE
CA000418563A CA1197509A (en) 1982-09-02 1982-12-24 Polymeric quaternary ammonium compounds and their uses
FR8222118A FR2532646B1 (en) 1982-09-02 1982-12-30 NOVEL POLYMERIC COMPOUNDS OF QUATERNARY AMMONIUM AND THEIR APPLICATIONS
AU91997/82A AU560802B2 (en) 1982-09-02 1982-12-31 Polymeric quaternary ammonium compounds
BE0/209953A BE895685A (en) 1982-09-02 1983-01-24 POLYMERIC QUATERNARY AMMONIUM COMPOUNDS
JP58021405A JPS5944350A (en) 1982-09-02 1983-02-10 Quaternary ammonium compound and use
AR292271A AR231124A1 (en) 1982-09-02 1983-03-02 POLYCUATERNARY AMMONIUM COMPOUNDS AND METHODS OF APPLICATION
IT47857/83A IT1165578B (en) 1982-09-02 1983-03-04 POLYMERIC COMPOUNDS OF QUATERNARY AMMONIUM AND THEIR USES
MX197623A MX166612B (en) 1982-09-02 1983-06-10 METHOD OF PREPARING A DICUATERNARY AMMONIUM COMPOSITION
GB08319310A GB2126579B (en) 1982-09-02 1983-07-18 Polymeric quaternary ammonium substituted ureas
BR8304165A BR8304165A (en) 1982-09-02 1983-08-03 METHOD OF PREPARING A QUATERNARY AMMONIUM POLYMERIC COMPOUND
CA000456480A CA1241653A (en) 1982-09-02 1984-06-13 Polymeric quaternary ammonium compounds, their preparation and use
AU29581/84A AU566275B2 (en) 1982-09-02 1984-06-20 Polymeric quaternary ammonium compounds
NL8401968A NL8401968A (en) 1982-09-02 1984-06-21 POLYMERIC QUATERARY AMMONIUM COMPOUNDS, METHOD FOR PREPARING THE SAME AND THEIR USES
GB08415965A GB2160538B (en) 1982-09-02 1984-06-22 Ionene-type polymers
FR8410019A FR2566414B1 (en) 1982-09-02 1984-06-25 POLYMERIC COMPOUNDS OF QUATERNARY AMMONIUM, THEIR PREPARATION AND THEIR USE
DE3423703A DE3423703C2 (en) 1982-09-02 1984-06-27 Polymers, quaternary ammonium compounds and their use
BE0/213246A BE900050A (en) 1982-09-02 1984-06-29 POLYMERIC COMPOSITIONS BASED ON QUATERNARY AMMONIUM DERIVATIVES, THEIR PREPARATION AND THEIR USE.
JP59140425A JPH0662514B2 (en) 1982-09-02 1984-07-06 Ionene type polymer
IT48577/84A IT1177902B (en) 1982-09-02 1984-07-17 POLYMERIC COMPOUNDS OF QUATERNARY AMMONIUM, THEIR PREPARATION AND THEIR USE
BR8403882A BR8403882A (en) 1982-09-02 1984-08-03 METHOD FOR PREPARING POLYMERIC COMPOUNDS

Applications Claiming Priority (6)

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US06/414,108 US4506081A (en) 1982-09-02 1982-09-02 Polymeric quaternary ammonium compounds and their uses
CA000456480A CA1241653A (en) 1982-09-02 1984-06-13 Polymeric quaternary ammonium compounds, their preparation and use
GB08415965A GB2160538B (en) 1982-09-02 1984-06-22 Ionene-type polymers
BE0/213246A BE900050A (en) 1982-09-02 1984-06-29 POLYMERIC COMPOSITIONS BASED ON QUATERNARY AMMONIUM DERIVATIVES, THEIR PREPARATION AND THEIR USE.
IT48577/84A IT1177902B (en) 1982-09-02 1984-07-17 POLYMERIC COMPOUNDS OF QUATERNARY AMMONIUM, THEIR PREPARATION AND THEIR USE
BR8403882A BR8403882A (en) 1982-09-02 1984-08-03 METHOD FOR PREPARING POLYMERIC COMPOUNDS

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GB2160538A true GB2160538A (en) 1985-12-24
GB2160538B GB2160538B (en) 1987-09-30

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AR (1) AR231124A1 (en)
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BE (2) BE895685A (en)
BR (2) BR8304165A (en)
CA (2) CA1197509A (en)
DE (2) DE3247536A1 (en)
FR (2) FR2532646B1 (en)
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MX166612B (en) 1993-01-21
AU560802B2 (en) 1987-04-16
AU9199782A (en) 1984-03-08
BR8304165A (en) 1984-04-24
DE3247536A1 (en) 1984-03-08
GB2126579A (en) 1984-03-28
GB2160538B (en) 1987-09-30
DE3423703A1 (en) 1986-01-02
AR231124A1 (en) 1984-09-28
BE895685A (en) 1983-05-16
GB8415965D0 (en) 1984-07-25
DE3247536C2 (en) 1993-07-29
CA1241653A (en) 1988-09-06
BR8403882A (en) 1986-03-11
IT8448577A0 (en) 1984-07-17
ZA829230B (en) 1983-10-26
JPS5944350A (en) 1984-03-12
FR2532646A1 (en) 1984-03-09
JPH0662514B2 (en) 1994-08-17
AU2958184A (en) 1986-01-02
US4506081A (en) 1985-03-19
NZ202707A (en) 1985-11-08
GB2126579B (en) 1986-02-05
IT8347857A0 (en) 1983-03-04
DE3423703C2 (en) 1995-05-18
GB8319310D0 (en) 1983-08-17
IT1165578B (en) 1987-04-22
FR2532646B1 (en) 1986-11-28
FR2566414B1 (en) 1989-01-06
JPS6118750A (en) 1986-01-27
BE900050A (en) 1984-10-15
IT1177902B (en) 1987-08-26
CA1197509A (en) 1985-12-03
FR2566414A1 (en) 1985-12-27

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